Ionic Properties Research Articles

Study on the Ionic Transport Properties of 3D Printed Concrete

Three-dimensional printed concrete (3DPC) is an anisotropic heterogeneous material composed of a concrete matrix and the interfaces between layers and filaments that form during printing. The overall ion transport properties can be characterized by the equivalent diffusion coefficient. This paper first establishes a theoretical model to calculate the equivalent diffusion coefficient of 3DPC. Verification through numerical calculations shows that this theoretical model is highly precise. Based on this, the model was used to analyze the effects of dimensionless interface parameters on the equivalent diffusion coefficients in different directions of 3DPC. Finally, the dynamic ionic transport properties of 3DPC were investigated through finite element numerical simulation. The results of the dynamic study indicate that interfaces have a significant impact on the ion distribution and its evolution within 3DPC. The product of the interface diffusion coefficient and interface size can represent the ionic transport capacity of an interface. The stronger the ionic transport capacity of an interface, the higher the ion concentration at that interface. Due to the “drainage” effect of lateral interfaces, the ion concentration in the middle of 3DPC with a smaller equivalent diffusion coefficient is higher than that in 3DPC with a larger equivalent diffusion coefficient.

Effect of Counterion Size on Knotted Polyelectrolyte Conformations.

Using Langevin dynamics simulations and a coarse-grained primitive model of electrolytes, we show that the behavior of knotted circular strong polyelectrolytes (PEs) in diluted aqueous solution is largely affected by the diameter of the counterions (CIs), σCI. Indeed, we observe that both gyration radius and knot length vary nonmonotonically with σCI, with both small and bulky CIs favoring knot localization, while medium-sized ones promote delocalized knots. We also show that the conformational change from delocalized to tight knots occurs via the progressive coalescence of the knot's essential crossings. The emerging conformers correspond to the minima of the free energy landscape profiled as a function of the knot length or PE size. We demonstrate that different conformational states can coexist, the transition between them appearing first-order-like and controlled by the enthalpic and entropic trade-off of the amount of CIs condensed on the PE. Such balance can be further altered by varying CI concentrations, thus providing an additional and more convenient tuning parameter for the system properties. Our results lay the foundation for achieving broader and more precise external adjustability of knotted PE size and shape by choosing the nature of its CIs. Thus, they offer new intriguing possibilities for designing novel PE-based materials that are capable of responding to changes in ionic solution properties.

ZnO Substitution in Argyrodite Li5.5+3xZnxP1‐xOxS4.5‐xBr1.5 Electrolyte with Enhanced Interface Performance for All‐Solid‐State Battery

AbstractArgyrodite sulfide solid electrolytes (SSEs) have been attracting more concentration in ionic conductivity, crystal structure, and mechanical properties. Nevertheless, shortcomings of SSEs like poor air‐vapor stability and interface reactions limit the wider application in batteries. Herein, a double‐element ZnO substitution strategy is applied to enhancing Li5.5PS4.5Br1.5 Argyrodite electrolyte structure stability and property, Li5.5PS4.5Br1.5 electrolyte with a small amount of ZnO substitution to P and S. Li5.5+3xZnxP1‐xOxS4.5‐xBr1.5 solid electrolytes have achieved improved performance, interface composition also has changed, and crystal structure is becoming more stable. Specifically, LPSBr1.5‐4 %ZnO exhibits the most promising comprehensive properties, more expanded lithium pathway and crystal cell size, 2.25 mS cm−1 ionic conductivity at 25 °C, 65 % electronic conductivity decline, and air stability enhancement. Moreover, LPSBr1.5‐4 %ZnO show decent lithium compatibility and dendrite suppression capability, LPSBr1.5‐4 %ZnO can continue cycling for more than 800 h at 0.1 mA cm−2 in Li symmetric cell, and critical current density has reached 1.4 mA cm−2. More importantly, an all‐solid‐state battery (ASSB) with LPSBr1.5‐4 %ZnO electrolyte can cycle with 130 mAh g−1 capacity and more than 120 cycles in LiCoO2|SSE|In‐Li cell. Our work might provide a strategy to promote structure stability and electrochemical durability, and how element substitution affects ionic transport pathway and crystal structure.

Asymmetric ionogel electrolyte with an ultrathin metal–organic framework layer for lithium dendrite inhibition in solid-state lithium-metal batteries

Solid-state electrolytes (SSEs) are used to prevent internal short circuits caused by the growth of lithium dendrites in solid-state lithium-metal batteries (SSLMBs). Ionogel electrolytes are new polymeric SSEs with outstanding processability, excellent flexibility, and superior ionic conductivity. Lithium-ion transport in ionogel electrolytes depends on ionic liquid (IL) content; however, increasing the IL content improves ionic conductivity but sharply decreases mechanical properties, thus limiting the ability to resist lithium dendrites. Thus, ionogel electrolytes must strike a balance between ionic conductivity and mechanical properties. Herein, we adopt a new strategy to suppress the growth of lithium dendrites by in situ polymerizing an ultrathin metal–organic framework (MOF) layer (9.8 μm) onto a highly ionic conductive ionogel electrolyte. The ionogel electrolyte provides an asymmetric SSE (ASSE) with a remarkable ionic conductivity of 4.8 × 10−4 S cm−1 (30 °C), whereas the ultrathin MOF layer regulates uniform dissolution/deposition of lithium and inhibits lithium dendrite growth, thereby increasing critical current density of the ASSE to 0.65 mA cm−2. An SSLMB assembled with the ASSE and LiFePO4 exhibits excellent performance and cycling stability, maintaining a specific capacity of 125.4 mAh g−1 after 500 cycles at 0.3C.

Bioinspired 3D printed elastomer-hydrogel hybrid with robust interfacial bonding for flexible ionotronics

Hydrogels are widely used in flexible ionotronics due to their continuous conductive phase and good biocompatibility. However, their poor mechanical properties affect their stability and lifespan. It is a significant challenge to prepare hydrogels with both high conductivity and mechanical strength, as improving the mechanical properties often results in a tighter network, which reduces electrical conductivity. Human skin is composed of a stiff collagen fibril scaffold for resisting external damage, and a soft matrix that detect various stimuli through ion transport. Herein, inspired by the structure of human skin, a hydrogel composite with remarkable mechanical properties, high ionic conductivity, and self-healing property is prepared. The composite structure with 3D printed elastomeric skeleton and hydrogel matrix, addresses both the contradiction between the ionic conductivity and mechanical properties of hydrogels, as well as the difficulty of realizing complex macrostructures of the skeleton. The issue of weak interface in composites is resolved by creating interfacial covalent bonds. The composite’s self-healing property, combined with a robust interface, ensure the stability and longevity of the composite when used as flexible sensors. This novel approach of creating robust interface is also employed in the encapsulation of hydrogels and the fabrication of flexible microcircuits.

Antioxidant Systematic Alteration Was Responsible for Injuries Inflicted on the Marine Blue Mussel Mytilus edulis Following Strontium Exposure.

The ionic properties of strontium (Sr), a significant artificial radionuclide in the marine environment, were estimated using a stable nuclide-substituting experimental system under controlled laboratory conditions. The bio-accumulation of Sr and its impacts, as well as any possible hidden mechanisms, were evaluated based on the physiological alterations of the sentinel blue mussel Mytilus edulis. The mussels were exposed to a series of stress-inducing concentrations, with the highest solubility being 0.2 g/L. No acute lethality was observed during the experiment, but sublethal damage was evident. Sr accumulated in a tissue-specific way, and hemolymph was the target, with the highest accumulating concentration being 64.46 µg/g wet weight (ww). At the molecular level, increases in the levels of reactive oxygen species (ROS) and malondialdehyde (MDA) and changes in ROS components (H2O2, O2-, and -OH) and antioxidant system activity indicated that the redox equilibrium state in hemocytes was disturbed. Furthermore, the rise in the hemocyte micronucleus (MN) rate (4‱ in the high-concentration group) implied DNA damage. At the cellular level, the structures of hemocytes were damaged, especially with respect to lysosomes, which play a crucial role in phagocytosis. Lysosomal membrane stability (LMS) was also affected, and both acid phosphatase (ACP) and alkaline phosphatase (AKP) activities were reduced, resulting in a significant decline in phagocytosis. The hemolymph population structure at the organ level was disturbed, with large changes in hemocyte number and mortality rate, along with changes in component ratios. These toxic effects were evaluated by employing the adverse outcome pathway (AOP) framework. The results suggested that the disruption of intracellular redox homeostasis is a possible explanation for Sr-induced toxicity in M. edulis.

Correction to “Review of Ionic Conductivity Properties of NASICON Type Inorganic Solid Electrolyte LATP”

Correction to “Review of Ionic Conductivity Properties of NASICON Type Inorganic Solid Electrolyte LATP”

Sol-gel synthesis of composite adsorbent coating from Prosopis juliflora–activated carbon for simultaneous adsorptive removal of Cd2+ and Cr2O72- from wastewater

ABSTRACT To overcome the challenges associated with powdered activated carbon (PAC) in water and wastewater treatment, the efficacy of composite adsorbent coating (CAC) synthesized using a simple sol-gel method with Prosopis juliflora-activated carbon for the simultaneous reduction of Cd2+ and Cr2O72− was investigated. The CAC was characterized by FTIR (C-H, C = O, and O-H stretching), pHPZC (6 -6.6), SEM (porous-rough surface), and BET surface area (10.6 m2/g) techniques. Statistical analysis confirmed that pH and contact time significantly (p < 0.0001) affected both metal ions removal, with Cd2+ removal generally exceeding that of Cr2O72− due to better ionic properties. Using the optimized conditions (8.5 pH, 0.25 dosage, 5 mg concentration, 105 minutes contact time and 23.73 °C temperature), the predicted and experimental ion removal efficiencies were 86.86 and 83.98% for Cd2+ and 94.26 and 58.08% for Cr2O72−, respectively. The Langmuir adsorption isotherm was the best-suited model (R2 > 0.99), while the metal ions removal was regulated by the PSO kinetic model (R2 > 0.999). The adsorption process was endothermic and spontaneous, as indicated by thermodynamic values (−ΔG°, +ΔH°, +ΔS°). The study demonstrates CAC's effectiveness as an alternative to PAC, offering significant advantages in removing metal ions from wastewater.

Defect Modulation via SnX2 Additives in FASnI3 Perovskite Solar Cells.

Tin halide perovskites suffer from high defect densities compared with their lead counterparts. To decrease defect densities, SnF2 is commonly used as an additive in tin halide perovskites. Herein, we investigate how SnF2 compares to other SnX2 additives (X = F, Cl, Br) in terms of electronic and ionic defect properties in FASnI3. We find that FASnI3 films with SnF2 show the lowest Urbach energies (EU) of 19 meV and a decreased p-type character, as probed with ultraviolet photoemission spectroscopy. The activation energy of ion migration, as probed with thermal admittance spectroscopy, for FASnI3 with SnF2 is 1.33 eV, which is higher than with SnCl2 and SnBr2, which are 1.22 and 0.79 eV, respectively, resulting in less ion migration. Because of improved defect passivation, the champion power conversion efficiency of FASnI3 with SnF2 is 7.47% and only 1.84% and 1.20% with SnCl2 and SnBr2, respectively.

Enhanced reactivity of Li+@C60 toward thermal [2 + 2] cycloaddition by encapsulated Li+ Lewis acid.

Lithium ion-endohedral fullerene (Li+@C60), a member of the burgeoning family of ion-endohedral fullerenes, holds substantial promise for diverse applications owing to its distinctive ionic properties. Despite the high demand for precise property tuning through chemical modification, there have been only a few reports detailing synthetic protocols for the derivatization of this novel material. In this study, we report the synthesis of Li+@C60 derivatives via the thermal [2 + 2] cycloaddition reaction of styrene derivatives, achieving significantly higher yields of monofunctionalized Li+@C60 compared to previously reported reactions. Furthermore, by combining experimental and theoretical approaches, we clarified the range of applicable substrates for the thermal [2 + 2] cycloaddition of Li+@C60, highlighting the expanded scope of this straightforward and selective functionalization method.

Polymer/cement composite electrolyte with high strength and high ionic conductivity for structural supercapacitors

All-solid-state structural supercapacitors (ASSC) based on polymer/cement electrolytes (PCE) are promising energy storage devices in buildings due to the tremendous demand for zero-energy buildings. However, the challenge of PCE remains in well balancing the mechanical properties and ionic conductivity. Herein, an integrated electro-mechanical PCE introducing PAM (20 wt%, synthesized by in-situ polymerization) and PAM (5 wt%, commercial) simultaneously largely improves the ionic conductivity (68.54 mS/cm) and mechanical properties (47.96 MPa). Surprisingly, PAM (20% wt%, in-situ polymerization synthesis) and PAM (5% wt%, commercial) were introduced simultaneously to modify PCE, which not only had a synergistic effect on compressive strength but also had a synergistic effect on ionic conductivity. Moreover, an assembled ASSC based on 20-AM-5-PAM PCE exhibits excellent performance with an areal energy density of 25.17 μWh/cm2 at a power density of 50 μW/cm2 and ～96% capacitance retention after 5000 cycles. These results demonstrate the great potential for the application of 20-AM-5-PAM PCE in high-strength and large-volume building structure energy storage devices.

Correlation between Ionic Conductivity and Mechanical Properties of Solid-like PEO-based Polymer Electrolyte.

Poly(ethylene glycol) methyl ether methacrylate polymer networks (PEO-based networks), with or without anionic bis(trifluoromethanesulfonyl)imide (TFSI)-grafted groups, are promising electrolytes for Li-metal all solid-state batteries. Nevertheless, there is a need to enhance our current understanding of the physicochemical characteristics of these polymer networks to meet the mechanical and ionic conductivity property requirements for Li battery electrolyte materials. To address this challenge, our goal is to investigate the impact of the cross-linking density of the PEO-based network and the ethylene oxide/lithium ratio on mechanical properties (such as glass transition temperature and storage modulus) and ionic conductivity. We have synthesized a series of cross-linked PEO-based polymers (si-SPE for single ion solid polymer electrolyte) via solvent-free radical copolymerization. These polymers are synthesized by using commercially available lithium 3-[(trifluoromethane)sulfonamidosulfonyl]propyl methacrylate (LiMTFSI), poly(ethylene glycol)methyl ether methacrylate (PEGM), and [poly(ethylene glycol) dimethacrylate] (PEGDM). In addition, we have synthesized a series of cross-linked PEO-based polymers (SPE for solid polymer electrolyte) using LiTFSI as the ionic species. Most of the resulting polymer films are amorphous, self-standing, flexible, homogeneous, and thermally stable. Interestingly, our research has revealed a correlation between ionic conductivity and mechanical properties in both the SPE and si-SPE series. Ionic conductivity increases as glass transition temperature, α relaxation temperature, and storage modulus decrease, suggesting that Li+ transport is influenced by polymer chain flexibility and Li+/EO interaction.

Methane foam performance evaluation in fractured oil-wet carbonate systems at elevated pressure and temperature conditions

This study investigates the potential of foam flooding for enhanced oil recovery in oil-wet fractured systems under reservoir conditions. Two surfactants with distinct ionic properties were employed in combination with methane to generate foam via simultaneous injection into propped fractures, aiming to optimize the diversion of gas from fractures to the matrix for improved oil recovery. Core flooding experiments demonstrated the critical roles of total injection rate and foam quality in controlling foam performance. Increasing the total injection rate from 1 to 3 cm³/min enhanced foam generation rates and foam lamella stability, facilitating better interactions between fractures and the matrix. However, beyond an injection rate of 4 cm³/min, there was a decline in apparent viscosity and mobility reduction factor. Foam strength was directly proportional to higher foam quality within the 50 to 80% range, but beyond 85% foam quality, fluctuations in pressure drop signaled the formation of weaker, less stable foams. Micro-scale experiments validated these macroscopic findings, revealing that smaller bubbles were associated with higher flow rates and lower foam qualities. This research contributes valuable insights into both micro and macro-scale in-situ foam generation, which can inform the design and application of foam-based enhanced oil recovery methods in fractured reservoirs.

Crystal structure, Hirshfeld surface analysis and ionic conduction properties of 4-(diphenylamino)benzaldehyde-4-(methyl)thiosemicarbazone additive with D-π-D molecular arrangement system

A new single crystal of 4-(diphenylamino)benzaldehyde-4-(methyl)thiosemicarbazone, featuring a D-π-D molecular template was synthesized and utilized as an additive in solid biopolymer electrolytes mixed with carboxymethyl cellulose (CMC) and propylene carbonate (PC). The additive was structurally characterized using single-crystal X-ray diffraction. This revealed a triclinic crystal structure belonging to the triclinic space group, P1−. The lattice parameters were determined as follows: a = 6.942(6) Å; b = 11.409(11) Å; c = 12.442(10) Å; α= 91.024(16)°; β= 104.264(12)°; γ= 107.496(12)°; V= 906.4(13)Å3 and Z= 2. Notably, the additive exhibited extensive π-electron delocalization, leading to the formation of infinite chains through C-H-π interactions and intermolecular hydrogen bonding, ultimately resulting in an inverse centrosymmetric dimer in the form of the R22(8) motif. Furthermore, a detailed Hirshfeld surface analysis of the additive revealed significant contributions from C···H/ H···C, H···S/S···H and H···N/ N···H interactions with 20.7%, 11.2% and 3.7% of the total Hirshfeld surface analysis, respectively. These interactions indicate the potential of the additive to facilitate efficient electron transfer processes. The conductivity (σ) of the CMC–PC–additive system determined at ambient temperature was 8.00 ×10−9 Scm−1. The dielectric properties showed that the system follows the non-Debye behavior, in which the conductivity is predominantly due to ion conduction via the hopping mechanism.

Triselenasumanene-based organic molecules as donor and hole-transporting materials for next-generation solar cells

The optoelectronic and charge transport properties of triselenasumanene-based organic molecules were studied using electronic structure calculations to explore their potential as a hole-transporting material (HTM) in perovskite solar cells (PSCs) and as electron donors in organic solar cells (OSCs). Based on the recently synthesized triselenasumanene (SESUM) molecule, nine molecules (SESUMXn, where X = anthracene (A), tetracene (T) and pentacene (P), n = number of attached A, T and P, i.e. 1, 2 and 3) were designed by extending the π-conjugation. The newly designed molecules possessed suitable energy-level alignment with the energy bands of commonly used perovskite material, CH3NH3PbI3, in PSCs, and are suitable as electron-donor material with the commonly used acceptor material, PC61BM, in OSCs. The calculated ionic state properties and electrophilicity index also showed that the studied molecules were potential donor materials for OSCs. Further, the calculated open circuit voltage and fill factor of SESUM and anthracene- and tetracene-substituted SESUM molecules were comparable with those of recently reported donor molecules. The calculated absorption spectra, effective hole transfer integral and stacking angle distribution showed the suitability of SESUMX2 and SESUMX3 molecules as HTM in PSCs. The results of periodic density functional theory calculations showed that the tri-substituted SESUM molecules, SESUMX3 (where, X = A, T and P), were effectively adsorbed on the CH3NH3PbI3 surface and abstracted the hole carrier from the perovskite surface.

Adsorption Removal Characteristics of Hazardous Metalloids (Antimony and Arsenic) According to Their Ionic Properties

Antimony and arsenic, which have a high carcinogenicity, should be removed depending on their ionic charge in water. Therefore, we attempted to confirm the adsorption characteristics of antimony and arsenic considering ionic charge to improve removal efficiency. We used palm-based activated carbon (PAC), coal-based activated carbon (CAC), modified activated carbon (MAC), styrene-divinylbenzene copolymer (SP825), activated alumina (AA), and zeolite as adsorbents for antimony and arsenic. Negatively charged adsorbents (CAC, PAC, MAC, and zeolite) with similar zeta potentials showed better removal efficiency as the surface area increased. However, SP825, which is almost neutral, and AA, which is positively charged, exhibited a high removal efficiency (100%) for arsenic and Sb(V), which are anions, regardless of surface area. However, due to the price, coal-based activated carbon or palm-based activated carbon is considered more advantageous than using AA or SP825. Last, during the arsenic adsorption process, As(III) was oxidized to As(V) due to Fe(II) contained in activated carbon. The addition of activated carbon can improve oxidation efficiencies of As(III) before coagulation and precipitation, in which As(V) is easier to remove than As(III).

Polydopamine-modified MXene/cellulose nanofibers composite film for self-powered humidity sensing and humidity actuating

Humidity sensors are of great significance in the domains of wearable electronic products, environmental and food quality monitoring, and human healthcare. In general, they necessitate an external power source in the form of a battery. Despite considerable efforts, developing self-powered sensing systems without reliance on an external power supply remains a major challenge. Herein, an electrochemical humidity sensor with primary battery structure based on redox reaction was designed, in which polydopamine (PDA)-modified MXene/TEMPO-oxidized cellulose nanofibers/LiCl (PDMM/TOCNFs/LiCl) composite film serves as electrolyte layer. The introduction of TOCNFs confers outstanding structural stability and superior tensile strength upon the composite film. Importantly, the hygroscopic and ionic conductivity properties of the PDMM/TOCNFs/LiCl electrolyte allow the sensor to generate spontaneous voltage over a wide relative humidity (RH) range of 11 – 91%. In addition, the developed sensor exhibits excellent humidity-sensing performances, including high voltage response, fast response/recovery time, and superior humidity-sensing stability. Moreover, mussel-inspired PDA improves the ambient stability of MXene by engineering interfacial interactions, which imparts the hygroscopic PDMM/TOCNFs/LiCl composite film with desirable stability for practical applications. Finally, the potential applications of the sensor and the composite film in human respiration, non-contact sensing, and humidity actuating are demonstrated. This work paves the way for the development of an innovative self-powered humidity sensing system.

The differences in bonding properties and electrical, thermal conductivity between the preferred crystallographic orientation interface of Cu3Sn/Cu

First-principles calculations based on Density-Functional theory and Semi-classical Boltzmann thermal transport theory have been applied to research the interfacial stability, electronic structures, bonding properties, and thermoelectric transport properties of different preferred crystallographic orientation interface of Cu3Sn/Cu. All interface models proved to have stable structures, the interfacial ideal adhesion of works of Cu3Sn (02¯5)/Cu (042) interface, Cu3Sn (100)/Cu (100) interface, and Cu3Sn <010>⊥Cu (100) interface are 1.956 J/m2, 1.182 J/m2, and 2.126 J/m2, respectively. The newly formed chemical bonds at the interface exhibit ionic and covalent properties. Moreover, the electrical conductivity and thermal conductivity of 16.787 × 108 S · m−1 and 1.136 × 104 W · m−1 · K−1 at 300 K for the Cu3Sn <010>⊥Cu (100) interface are superior than the other two Cu3Sn/Cu interfaces.

DIW 3D Printing Aligned Catkins to Access Significant Enhanced Responsive Ionogel

AbstractAlthough stimuli‐responsive gels have received significant attention due to their flexible structure and high tolerance to various stimuli, the high solvent content leads to relatively low mechanical properties and instability in performance due to water evaporation. This limits their application to some extent. Here, catkins enhanced ionogel is crafted that prevents solvent vaporization‐induced properties from abating yet remains humidity responsiveness. By using direct ink writing (DIW) 3D printing, the catkins can be aligned within the ionogel, resulting in a significant increase in ionic conductivity (0.17 S·cm−1) and mechanical properties (4.75 times). Moreover, the environment stability (−50–150 °C) and hygroscopicity of the ionic liquid (IL) allow the 3D‐printed composite to perform a controllable lubrication behavior in response to changes in humidity and temperature. This work demonstrates the significant enhancement of responsive ionogels through DIW 3D printing with aligned catkins and presents a new strategy for achieving the lubricating regulation.

Production of carbon nanotube-supported metal (M = Ru, Pd, Pt) doped polyacrylic acid electrode materials and supercapacitor application

A radical polymerization with the contribution of carbon nanotube (CNT) supported metal (M/CNT) catalysts has been reported on the preparation of poly(acrylic acid) (PAAc) hydrogels for supercapacitor electrode materials. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) and mapping, micro-Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) are used to characterize the hydrogels. The obtained PAAc-g-(Ru/CNT) as a supercapacitor electrode shows a high specific capacitance of 1294.5 F g−1 at 5.0 mV s−1. This electrode has a high capacitance retention of up to 97.7 % after 1000 cycles, showing extended cycle life and strong electrochemical stability. Furthermore, the idea of such a synthesis technique can be extended to include the co-use of polymers and other materials with ionic conductivity properties with electrocatalysts for metal oxide supercapacitors and advanced energy storage devices.